EP2335797B1 - Structure en nid d'abeilles en céramique - Google Patents
Structure en nid d'abeilles en céramique Download PDFInfo
- Publication number
- EP2335797B1 EP2335797B1 EP09802754.3A EP09802754A EP2335797B1 EP 2335797 B1 EP2335797 B1 EP 2335797B1 EP 09802754 A EP09802754 A EP 09802754A EP 2335797 B1 EP2335797 B1 EP 2335797B1
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- EP
- European Patent Office
- Prior art keywords
- ceramic honeycomb
- less
- pores
- honeycomb structure
- pore
- Prior art date
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- 239000000919 ceramic Substances 0.000 title claims description 100
- 239000011148 porous material Substances 0.000 claims description 175
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 118
- 238000009826 distribution Methods 0.000 claims description 54
- 210000002421 cell wall Anatomy 0.000 claims description 32
- 230000001186 cumulative effect Effects 0.000 claims description 20
- 210000004027 cell Anatomy 0.000 claims description 18
- 229910052878 cordierite Inorganic materials 0.000 claims description 18
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 16
- 230000035699 permeability Effects 0.000 claims description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052596 spinel Inorganic materials 0.000 claims description 8
- 239000011029 spinel Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 description 115
- 239000000463 material Substances 0.000 description 51
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- 238000005245 sintering Methods 0.000 description 11
- 239000004071 soot Substances 0.000 description 11
- 239000005995 Aluminium silicate Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 235000012211 aluminium silicate Nutrition 0.000 description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 230000002542 deteriorative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 7
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- 230000035939 shock Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 239000013618 particulate matter Substances 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 229910052753 mercury Inorganic materials 0.000 description 5
- 230000002093 peripheral effect Effects 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
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- 230000005484 gravity Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000010431 corundum Substances 0.000 description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- 238000004140 cleaning Methods 0.000 description 2
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 1
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
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- 238000011835 investigation Methods 0.000 description 1
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- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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- NOTVAPJNGZMVSD-UHFFFAOYSA-N potassium monoxide Inorganic materials [K]O[K] NOTVAPJNGZMVSD-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/06—Ceramic, e.g. monoliths
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/30—Honeycomb supports characterised by their structural details
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24149—Honeycomb-like
Definitions
- the present invention relates to a ceramic honeycomb structure used for ceramic honeycomb filters for removing particulate matter from an exhaust gas discharged from diesel engines.
- PM-capturing ceramic honeycomb filters are conventionally mounted in exhaust pipes connected to diesel engines.
- One example of ceramic honeycomb filters for capturing PM to clean exhaust gases is shown in Figs. 1(a) and 1(b) .
- the ceramic honeycomb filter 10 comprises a ceramic honeycomb structure comprising porous cell walls 2 defining many outlet-side-sealed flow paths 3 and inlet-side-sealed flow paths 4 and a peripheral wall 1, and upstream-side plugs 6a and downstream-side plugs 6c for alternately sealing the inlet-side end surfaces 8 of the inlet-side-sealed flow paths 4 and the outlet-side end surfaces 9 of the outlet-side-sealed flow paths 3 in a checkerboard pattern.
- this ceramic honeycomb filter 10 is held in a metal container 12 with support members 14, and longitudinally sandwiched by support members 13a, 13b.
- the support members 14 are generally formed by a metal mesh and/or a ceramic mat.
- the ceramic honeycomb filter 10 attached to a diesel engine is subject to mechanical vibration and shock from the engine, the road, etc. via the support members 13a, 13b, 14.
- large ceramic honeycomb filters of more than 200 mm in outer diameter for use in large vehicles or special vehicles are subject to large vibration and shock, they are required to keep enough strength.
- Important characteristics among those required for ceramic honeycomb filters are particulate-matter-capturing efficiency, pressure loss, and particulate-matter-capturing time (a time period from the start of capturing to a point reaching a constant pressure loss).
- the capturing efficiency and the pressure loss are in a contradictory relation; the higher capturing efficiency resulting in larger pressure loss and a shorter capturing time, and smaller pressure loss resulting in a longer capturing time and poorer capturing efficiency.
- investigation has conventionally been conducted to provide technologies for controlling the porosities, average pore sizes and pore sizes on the cell wall surfaces of ceramic honeycomb structures.
- exhaust-gas-cleaning apparatuses comprising both SCR apparatuses for removing NOx and honeycomb filters for removing particulate matter have been investigated, and honeycomb filters are required to have smaller pressure loss than conventional ones. Because ceramic honeycomb filters of more than 200 mm in outer diameter for use in large vehicles or special vehicles do not easily have enough strength to withstand mechanical vibration and shock during use, ceramic honeycomb filters having sufficient strength and pressure loss characteristics cannot be obtained by conventional technologies as shown below.
- JP 61-129015 A discloses an exhaust-gas-cleaning filter having large pores having diameters of 40-100 ⁇ m, and small pores having diameters of 5-40 ⁇ m as many as 5-40 times the large pores on cell wall surfaces, this filter having high capturing efficiency from an early stage of use, and small pressure loss. It is further described that pores in cell walls preferably have an average pore size of more than 15 ⁇ m, and a cumulative pore volume of 0.3-0.7 cm 3 /g. The cumulative pore volume of 0.3-0.7 cm 3 /g is converted to porosity of 42.8-63.6% by volume. From a pore size distribution line shown in Fig.
- the honeycomb filters of Examples 1, 2, 5 and 6 have cumulative pore volumes of 0.58 cm 3 /g (porosity: 59%), 0.4 cm 3 /g (porosity: 50%), 0.7 cm 3 /g (porosity: 64%) and 0.3 cm 3 /g (porosity: 43%), respectively, and average pore sizes of 40 ⁇ m, 35 ⁇ m, 44 ⁇ m and 15 ⁇ m, respectively.
- the honeycomb filters of Examples 1, 2 and 5 of JP 61-129015 A do not have enough strength because of too large average pore sizes or porosity, and the honeycomb filter of Example 6 has insufficient pressure loss characteristics because of too small porosity. Namely, the honeycomb filters of Examples 1, 2, 5 and 6 do not have both small pressure loss and high strength.
- JP 2002-219319 A discloses that porous honeycomb filters have high particulate-matter-capturing efficiency without pressure loss increase due to the clogging of pores, when their cell walls have such pores that the volume of pores having diameters of less than 10 ⁇ m is 15% or less, the volume of pores having diameters of 10-50 ⁇ m is 75% or more, and the volume of pores having diameters of more than 50 ⁇ m is 10% or less, based on the total pore volume.
- the pore structure described in JP 2002-219319 A fails to provide sufficient pressure loss characteristics and strength to large ceramic honeycomb filters of more than 200 mm in outer diameter for use in large vehicles or special vehicles.
- JP 2004-322082 A discloses a ceramic honeycomb filter wherein the total pore volume is 0.55-0.80 cm 3 /g (corresponding to porosity of 59-67%), and the volume of pores of 100 ⁇ m or more is 0.02-0.10 cm 3 /g.
- the pore structure described in JP 2004-322082 A need to be improved on pressure loss characteristics and strength to withstand mechanical vibration and shock during use, particularly for large ceramic honeycomb filters of more than 200 mm in outer diameter for large vehicles or special vehicles.
- the pore structure described in JP 2005-530616 A is not satisfactory in both pressure loss characteristics and strength, particularly when used for large ceramic honeycomb filters of more than 200 mm in outer diameter for large vehicles or special vehicles.
- the pore structure described in JP 2007-525612 A does not have sufficient pressure loss characteristics and strength particularly when used for large ceramic honeycomb filters of more than 200 mm in outer diameter for large vehicles or special vehicles.
- WO 2005/090263 A discloses a method for producing a porous ceramic body by forming a moldable ceramic material containing porous silica powder or porous silica-containing compound powder into a predetermined shape, and sintering it. It describes that porous silica powder or porous silica-containing compound powder functions as a pore-forming material for controlling the size and amount of pores.
- the silica particles described in WO2005/090263 A have a wide particle size distribution, with many coarse particles even when particles of the optimum median diameter are selected, forming cell walls having large pores. As a result, it does not have enough strength to withstand vibration and shock when mounted on vehicles.
- EP 2 228 115 , EP 2 011 775 and WO 01/91882 also disclose ceramic honeycomb structures.
- an object of the present invention is to provide a ceramic honeycomb filter suffering small pressure loss and having enough strength in use.
- the ceramic honeycomb structure of the present invention is defined as in claim 1.
- the porous cell walls preferably have air permeability of 4 x 10 -12 m 2 to 9 x 10 -12 m 2 .
- the ceramic honeycomb structure of the present invention preferably has isostatic strength of 1 MPa or more.
- the porous cell walls preferably have a thickness of 0.2-0.3 mm and a cell density of 23-39 cells/cm 2 .
- the pressure loss is preferably 1.2 kPa or less, when capturing 2 g/liter of soot at a flow rate of 10 Nm 3 /min with a ceramic honeycomb filter obtained by alternately plugging flow path ends of a ceramic honeycomb structure of 266.7 mm in diameter and 304.8 mm in length having a cell density of 36.4 cells/cm 2 and a cell wall thickness of 0.28 mm in a checkerboard pattern.
- a main component of a crystal phase in the ceramic honeycomb structure of the present invention is cordierite, preferably containing 3-6% of spinel and 1-8% of cristobalite.
- the thermal expansion coefficient between 20°C and 800°C is preferably 3 x 10 -7 -13 x 10 -7 .
- the pore-forming material is preferably 1-15% based on the cordierite-forming material, and the pore-forming material is preferably in the form of powder having a mode diameter of 30-70 ⁇ m and a particle size distribution deviation SD of 0.5 or less.
- , is preferably 15 ⁇ m or less.
- the silica particles preferably have sphericity of 0.5 or more.
- the pore-forming material is preferably more than 6% and 15% or less, based on the cordierite-forming material.
- the ceramic honeycomb structure of the present invention has a well-balanced pressure loss characteristics and strength, by lowering the percentage of coarse pores which would deteriorate pressure loss characteristics, and the percentage of fine pores which would deteriorate strength.
- This ceramic honeycomb structure can provide a ceramic honeycomb filter with reduced pressure loss and increased strength.
- the ceramic honeycomb filter suffers large pressure loss.
- the porosity exceeding 68% provides decreased strength.
- the porosity of the porous cell walls is preferably more than 58% and 66% or less, most preferably, 59-66%.
- the average pore size is 15-32 ⁇ m.
- the average pore size of less than 15 ⁇ m provides increased pressure loss, and the average pore size exceeding 35 ⁇ m provides decreased strength.
- the average pore size is preferably 25-32 ⁇ m.
- the volume of pores having diameters of more than 50 ⁇ m is more than 10% and 25% or less of the total pore volume.
- the volume of pores having diameters exceeding 50 ⁇ m is 10% or less, the ceramic honeycomb structure has deteriorated pressure loss characteristics.
- the percentage of coarse pores lowering the strength increases, providing the ceramic honeycomb structure with low strength.
- the volume of pores having diameters of more than 50 ⁇ m is preferably 11-24%, more preferably 12-23%.
- the volume of pores having diameters of 100 ⁇ m or more is 1-8% of the total pore volume.
- the volume of pores having diameters of 100 ⁇ m or more is less than 1%, there are a high percentage of fine pores deteriorating pressure loss characteristics. When it exceeds 8%, there are a high percentage of coarse pores lowering the strength, so that the ceramic honeycomb structure does not have enough strength in use.
- the volume of pores having diameters of 100 ⁇ m or more is preferably 2-7%.
- the volume of pores having diameters of less than 10 ⁇ m is 3-10% of the total pore volume. Pores having diameters of less than 10 ⁇ m secure communications through larger pores, improving the pressure loss characteristics. When the volume of pores having diameters of less than 10 ⁇ m is less than 3%, sufficient communications through pores cannot be obtained, resulting in large pressure loss. When it exceeds 10%, the percentage of pores having diameters of more than 10 ⁇ m is relatively low despite enough communications, resulting in the deteriorated pressure loss.
- the volume of pores having diameters of less than 10 ⁇ m is preferably 4-8%.
- the pore structure of cell walls has the above porosity, average pore size and pore size distribution, with a pore size distribution deviation ⁇ of 0.45 or less, there is a large percentage of pores having diameters of 15-35 ⁇ m, resulting in a sharp pore size distribution.
- Cell walls having such pore structure have small pressure loss and high strength.
- the pore size distribution deviation exceeds 0.45, the percentage of pores deteriorating pressure loss characteristics and strength increases, failing to obtain ceramic honeycomb filters meeting both conditions of strength and pressure loss characteristics.
- the pore size distribution deviation ⁇ is preferably 0.43 or less, more preferably 0.40 or less.
- D 80 ⁇ D 20 .
- the cumulative pore volume relative to the pore size can be measured by mercury porosimetry, particularly by a mercury porosimeter.
- Cell walls having the above porosity, average pore size, pore size distribution and pore size distribution deviation contain pores effective for improving pressure loss characteristics and pores effective for improving strength in good balance, providing the air permeability of 4 x 10 -12 m 2 to 9 x 10 -12 m 2 .
- the air permeability is more preferably 5 x 10 -12 m 2 to 8 x 10 -12 m 2 .
- the ceramic honeycomb structure preferably has isostatic strength of 1 MPa or more. When the isostatic strength is less than 1 MPa, the ceramic honeycomb structure is likely to have insufficient strength in use.
- the isostatic strength is preferably 2 MPa or more.
- the cell walls preferably have a thickness of 0.2-0.3 mm, and a cell density of 23-39 cells/cm 2 .
- the thickness of the cell walls is less than 0.2 mm, the cell walls have low strength.
- the ceramic honeycomb structure suffers increased pressure loss.
- the cell density is less than 23 cells/cm 2 , the cell walls have low strength.
- the ceramic honeycomb structure suffers increased pressure loss.
- a ceramic honeycomb filter obtained by plugging flow path ends of a ceramic honeycomb structure of 266.7 mm in diameter and 304.8 mm in length having a cell density of 36.4 cells/cm 2 and a cell wall thickness of 0.28 mm alternately in a checkerboard pattern preferably has a pressure loss of 1.2 kPa or less, when 2 g/liter of soot (2 g of soot per a filter volume of 1 liter) is captured at a flow rate of 10 Nm 3 /min. When the pressure loss exceeds 1.2 kPa to capture 2 g/liter of soot, the pressure loss is undesirably large.
- the pressure loss when 2 g/liter of soot is captured is more preferably 1 kPa or less.
- a crystal phase is mainly composed of cordierite, containing 3-6% of spinel and 1-8% of cristobalite, size change (expansion) by sintering can be minimized.
- Spinel and cristobalite in the crystal phase are more preferably 4-5% and 2-7%, respectively.
- the crystal phase may additionally contain mullite, corundum, tridymite, etc.
- the ceramic honeycomb structure has a thermal expansion coefficient in a range of 3 x 10 -7 to 13 x 10 -7 between 20°C and 800°C, it has sufficient heat shock resistance even when it is used as a ceramic honeycomb filter for diesel engines, etc.
- the thermal expansion coefficient is preferably 3.5 x 10 -7 to 11 x 10 -7 , more preferably 4 x 10 -7 to 10 x 10 -7 .
- the pressure loss can be suppressed.
- the area ratio A 0 /A is preferably 55 or less, more preferably 45 or less.
- the ceramic honeycomb structure is produced by extrusion-molding a moldable material comprising a cordierite-forming material and a pore-forming material, heating the resultant molding to the highest temperature of 1380-1435°C at a speed of 2-100°C/hour, sintering it at the highest temperature for 5-30 hours, and then cooling it to 1000°C at a speed of less than 100°C/hour.
- the cordierite-forming material comprises 10-20% of silica powder having a mode diameter of 30-60 ⁇ m, particles having particle sizes of 20 ⁇ m or less being 2-10%, particles having particle sizes of 100 ⁇ m or more being 2-10%, and particles having particle sizes of 200 ⁇ m or more being 1% or less.
- the silica powder having a relatively large particle size distribution makes a cordierite-forming sintering reaction slow, forming other crystals than cordierite, such as 3-6% of spinel and 1-8% of cristobalite. Accordingly, the crystal size can be stably controlled with small size change (mainly expansion due to the formation of cordierite) by sintering.
- Ceramics whose main crystal is cordierite, have pores formed by consuming the silica source material in a sintering process.
- the silica source material is more stable at high temperatures than other starting materials, so that it is melted and diffused at 1300°C or higher, forming pores.
- the addition of 10-20% of silica to the cordierite-forming material provides a preferred pore structure.
- the silica content exceeds 20%, the amounts of other silica source materials such as kaolin, talc, etc. should be decreased to maintain the state that the main crystal is cordierite. As a result, sufficiently low thermal expansion in an extrusion-molding direction cannot be obtained, resulting in low heat shock resistance.
- the silica content is less than 10%, the ceramic honeycomb structure has a small amount of pores, resulting in poor pressure loss characteristics.
- the silica content is preferably 13-18%.
- silica particles having the optimum mode diameter and particle size distribution provides a ceramic honeycomb structure with the optimum pore structure.
- This ceramic honeycomb structure in turn provides a ceramic honeycomb filter having small pressure loss and sufficient strength in use.
- the ceramic honeycomb structure When the mode diameter of silica is less than 30 ⁇ m, the ceramic honeycomb structure has many fine pores deteriorating the pressure loss characteristics. When the mode diameter of silica exceeds 60 ⁇ m, the ceramic honeycomb structure has many coarse pores decreasing the strength.
- the mode diameter of silica is preferably 5-55 ⁇ m.
- the mode diameter means a particle size whose volume is the maximum in a volume-based particle size distribution as shown in Fig. 5 .
- More than 1% of silica particles having particle sizes of 10 ⁇ m or less provide more fine pores deteriorating the pressure loss characteristics.
- the amount of silica particles having particle sizes of 10 ⁇ m or less is preferably 0.5% or less.
- More than 10% of silica particles having particle sizes of 20 ⁇ m or less make the percentage of pores of less than 10 ⁇ m in diameter higher and that of pores of more than 10 ⁇ m in diameter smaller, so that the ceramic honeycomb filter has poor pressure loss characteristics.
- the amount of silica particles having particle sizes of 20 ⁇ m or less is less than 2%, the volume of pores of less than 10 ⁇ m in diameter is less than 3% of the total pore volume, resulting in insufficient communications of pores and thus poor pressure loss characteristics.
- the amount of silica particles having particle sizes of 20 ⁇ m or less is preferably 3-9%.
- the ceramic honeycomb structure has many coarse pores, resulting in low strength.
- the amount of silica particles having particle sizes of 100 ⁇ m or more is preferably 5% or less, and the amount of silica particles having particle size of 200 ⁇ m or more is preferably 0.8% or less.
- the particle size distribution deviation SD of silica is 0.5 or less, providing a sharp pore size distribution, small pressure loss, and a smaller percentage of pores deteriorating the strength.
- d 20 represents a particle size ( ⁇ m) corresponding to a cumulative volume of 20%
- d 80 represents a particle size ( ⁇ m) corresponding to a cumulative volume of 80%
- a curve cumulative particle size distribution curve showing the relation between a particle size and a cumulative volume expressed by the volume percentage of particles having a particular particle size or less as shown in Fig. 4 , and d 20 ⁇ d 80 .
- the particle size can be measured by a particle size distribution meter (Microtrack MT3000).
- the particle size distribution deviation SD exceeding 0.5 provides a broad particle size distribution, resulting in a broad pore size distribution. As a result, the percentage of pores deteriorating the pressure loss characteristics and the strength increases, failing to achieve both small pressure loss and high strength.
- the particle size distribution deviation SD is preferably 0.4 or less, more preferably 0.3 or less.
- Silica particles with the above particle size distribution can be obtained by classification, mixing of pluralities of silica particles having arbitrary particle sizes, or pulverization under the optimized conditions.
- the silica particles may be crystalline or amorphous, though amorphous silica is preferable from the aspect of particle size distribution control.
- Amorphous silica can be obtained by pulverizing an ingot formed by melting high-purity, natural silica stone at high temperatures.
- Silica particles may contain Na 2 O, K 2 O, CaO, etc. as impurities, but the total amount of the impurities is preferably 0.1% or less to avoid a large thermal expansion coefficient.
- the pore-forming material is preferably 1-15% based on the cordierite-forming material. In the sintering process of cordierite ceramics, the pore-forming material is burned out before cordierite is synthesized, forming pores. When the pore-forming material is less than 1%, a small amount of pores are formed by the pore-forming material, resulting in poor pressure loss characteristics. When the pore-forming material exceeds 15%, too many pores are formed, failing to keep sufficient strength.
- the pore-forming material is preferably more than 6% and 15% or less, more preferably 6.1-14%, most preferably 6.5-13%.
- the pore-forming material may be known flour, graphite, starch, foaming resins such as polyethylene, polyethylene terephthalate and acrylic microcapsules, etc. Among them, the foaming resins of methyl methacrylate-acrylonitrile copolymers are preferable. the foaming resins may be before or after foaming, but foamed resins are preferable.
- the pore-forming material particles preferably have a mode diameter of 30-70 ⁇ m.
- the mode diameter of the pore-forming material particles is preferably 40-60 ⁇ m.
- the particle size distribution deviation SD of the pore-forming material is preferably 0.5 or less.
- a pore-forming material having a particle size distribution deviation SD of 0.5 or less provides a sharp pore size distribution, resulting in small pressure loss and a small percentage of pores deteriorating strength.
- porous cell walls having the optimum pore structure are formed, providing a ceramic honeycomb structure having small pressure loss and high strength.
- a particle size distribution deviation SD of the pore-forming material exceeding 0.5 provides a broad particle size distribution, resulting in a broad pore size distribution. As a result, the percentage of pores deteriorating pressure loss characteristics and strength increases, failing to achieve small pressure loss and high strength.
- the particle size distribution deviation SD of the pore-forming material is preferably 0.4 or less.
- is preferably 15 ⁇ m or less.
- of 15 ⁇ m or less provides uniform particle size distributions of silica and the pore-forming material, so that pores formed by sintering silica, etc. in cordierite ceramics and pores formed by burning the pore-forming material have similar distribution. As a result, the pressure loss characteristics are improved, and the percentage of pores having no adverse influence on the strength increases, providing a ceramic honeycomb structure with small pressure loss and high strength.
- is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, most preferably 6 ⁇ m or less.
- , may be 15 ⁇ m or less.
- Silica particles preferably have sphericity of 0.5 or more. When the sphericity is less than 0.5, there are a high percentage of fine pores adversely affecting pressure loss characteristics, and there are also many coarse pores lowering the strength.
- the sphericity is preferably 0.6 or more, more preferably 0.7 or more.
- the sphericity of silica particles is determined by averaging ratios of the projected areas of 20 particles determined by image analysis on an electron photomicrograph to the areas of circles each having a diameter equal to a maximum length of each particle between two points on its circumference at which a straight line passing its center of gravity crosses.
- High-sphericity silica particles are preferably spherical amorphous silica as shown in Fig. 6 .
- the spherical silica particles are obtained by spraying finely pulverized, high-purity, natural silica stone into a high-temperature flame to simultaneously melt and spheroidize silica particles.
- the particle sizes of spherical silica particles are controlled preferably by classification, etc.
- the cordierite-forming material is obtained by mixing starting material powders comprising a silica source, an alumina source and a magnesia source, such that its main crystal is cordierite whose main components are 42-56% by mass of SiO 2 , 30-45% by mass of Al 2 O 3 , and 12-16% of MgO.
- the silica source comprises kaolin powder, talc powder, etc. in addition to the above silica powder.
- the alumina source is preferably aluminum hydroxide and/or aluminum oxide because of few impurities.
- the total amount of Na 2 O, K 2 O and CaO in aluminum hydroxide or aluminum oxide is preferably 0.5% or less by mass, more preferably 0.3% or less by mass, most preferably 0.1% or less by mass.
- the amount of aluminum hydroxide, if used, in the cordierite-forming material is preferably 6-42% by mass, more preferably 6-15% by mass, most preferably 8-12% by mass.
- the amount of aluminum oxide, if used, in the cordierite-forming material is preferably 30% or less by mass, more preferably 12-25% by mass, most preferably 20-24% by mass.
- the alumina source preferably has an average particle size of 0.5-5 ⁇ m in the case of aluminum hydroxide, and 2-10 ⁇ m in the case of aluminum oxide. Because aluminum oxide retains its form up to relatively high temperatures during sintering, its particle size distribution affects the pore size distribution of the sintered ceramic honeycomb structure.
- aluminum oxide powder comprising 5% or less by mass of powder having a particle size of 45 ⁇ m or more, 2-22% by mass of powder having a particle size of 20 ⁇ m or more, 13-33% by mass of powder having a particle size of 10 ⁇ m or more, 40-68% by mass of powder having a particle size of 5 ⁇ m or more, and 50% or more of powder having a particle size of 2 ⁇ m or more.
- the kaolin powder is preferably 1-15% by mass.
- the addition of more than 15% by mass of kaolin powder makes it difficult to control the ceramic honeycomb structure to have 10% or less of pores having diameters of less than 10 ⁇ m, and the addition of less than 1% by mass of kaolin powder provides the ceramic honeycomb structure with a large thermal expansion coefficient.
- the kaolin powder content is more preferably 4-8% by mass.
- the magnesia source may be talc, magnesite, magnesium hydroxide, etc., and talc is preferable to reduce the thermal expansion coefficient.
- talc is preferably in the form of planar particles.
- a shape coefficient indicating the flatness of talc particles is preferably 0.77 or more, more preferably 0.8 or more, most preferably 0.83 or more.
- the magnesia source such as talc may contain Fe 2 O 3 , CaO, Na 2 O, K 2 O, etc. as impurities.
- the Fe 2 O 3 content in the magnesia source is preferably 0.5-2.5% by mass.
- the total amount of Na 2 O, K 2 O and CaO is preferably 0.50% or less by mass.
- the mixing of a cordierite-forming material containing silica particles, a pore-forming material, a binder, etc. is preferably conducted by a means having no pulverization media (Henschel mixer, etc.) to avoid silica particles, particularly amorphous silica particles, from being pulverized.
- An extrusion-moldable material is preferably blended by a means using no excess shearing (kneader, etc.).
- silica particles having a desired particle size distribution and particle shapes can exist without change in extrusion-molded products, resulting in a ceramic honeycomb structure having a desired pore size distribution and thus small pressure loss and high strength.
- the above mixing method and kneading method are effective.
- silica particles are destroyed during a mixing process, failing to obtain the desired pore size distribution.
- the ceramic honeycomb structure of the present invention can be formed into a ceramic honeycomb filter with both ends of flow paths plugged alternately in a checkerboard pattern, or a ceramic honeycomb filter with plugs inside flow paths.
- This cordierite-forming material powder was mixed with a foamed resin (pore-forming material) and methylcellulose (binder), and kneaded together with water to form a moldable ceramic material comprising the cordierite-forming material.
- This moldable material was extrusion-molded to a honeycomb structure, dried, deprived of a peripheral portion by machining, and sintered by heating from 1000°C to 1410°C at a speed of 20°C/h, keeping the highest temperature of 1410°C for 24 hours, and cooling from 1410°C to 1000°C at a speed of 50°C/h, for 200 hours in total, in the air.
- a periphery of the sintered ceramic honeycomb was coated with a skin layer comprising amorphous silica and colloidal silica, and dried to obtain a ceramic honeycomb structure of 266.7 mm in outer diameter and 304.8 mm in length having a cell density of 39 cells/cm 2 and a cell wall thickness of 0.30 mm.
- the mode diameter, the percentage of particle sizes of 20 ⁇ m or less, the percentage of particle sizes of 100 ⁇ m or more, and the percentage of particle sizes of 200 ⁇ m or more were determined from a particle size distribution measured by a particle size distribution meter (Microtrack MT3000).
- the sphericity of silica particles was determined by averaging ratios of the projected areas of 20 particles determined by image analysis on an electron photomicrograph to the areas of circles each having a diameter equal to a maximum length of each particle between two points on its circumference at which a straight line passing its center of gravity crossed.
- the average particle sizes of kaolin powder, talc powder, alumina powder and aluminum hydroxide powder were measured by a particle size distribution meter (Microtrack MT3000).
- Flow path ends of the ceramic honeycomb structure were plugged with a cordierite-forming material slurry alternately in a checkerboard pattern, dried, and sintered to produce a cordierite-based ceramic honeycomb filter.
- the length of each plug in a flow path direction was adjusted to 7-10 mm.
- Ceramic honeycomb filters were produced in the same manner as in Example 1, except for changing the silica powder, the kaolin powder, the talc powder, the alumina powder, the aluminum hydroxide powder and the pore-forming material as shown in Table 1, and changing the cell wall thickness and the cell density as shown in Table 2.
- the amount of each crystal was determined by dividing the X-ray diffraction intensity of each crystal by the total X-ray diffraction intensity of cordierite, spinel, cristobalite, corundum and mullite [X-ray diffraction intensity of (102) plane of cordierite + X-ray diffraction intensity of plane (220) of spinel + X-ray diffraction intensity of (220) plane of cristobalite + X-ray diffraction intensity of (104) plane of corundum + X-ray diffraction intensity of (110) plane of mullite].
- the amounts of cordierite, spinel and cristobalite are shown in Table 2.
- the air permeability was measured by Perm Automated Porometer (registered trademark) version 6.0 (available from Porous Materials, Inc.) at an air flow rate from 30 cc/sec to 400 cc/sec.
- the maximum air permeability in this range was evaluated by the following standard: Excellent The maximum air permeability was 5 x 10 -12 m 2 to 8 x 10 -12 m 2 . Good The maximum air permeability was 4 x 10 -12 m 2 or more and less than 5 x 10 -12 m 2 , or more than 8 x 10 -12 m 2 and 9 x 10 -12 m 2 or less. Poor The maximum air permeability was less than 4 x 10 -12 m 2 or more than 9 x 10 -12 m 2 .
- Carbon powder having particle sizes of 0.042 ⁇ m was supplied at a speed of 3 g/h to a ceramic honeycomb filter fixed to a pressure-loss-testing stand together with air at a flow rate of 10 Nm 3 /min, to measure pressure difference (pressure loss) between the inlet and outlet sides of the filter when the amount of soot accumulated reached 2 g per 1 liter of a filter volume.
- the pressure loss when capturing soot was evaluated by the following standard: Excellent The pressure loss was 1.2 kPa or less. Good The pressure loss was more than 1.2 kPa and 1.5 kPa or less. Poor The pressure loss was more than 1.5 kPa.
- the porosity, the average pore size, the volume of pores having diameters of less than 10 ⁇ m, the volume of pores having diameters of more than 50 ⁇ m, and the volume of pores having diameters of 100 ⁇ m or more were measured by mercury porosimetry.
- a test piece (10 mm x 10 mm x 10 mm) cut out of each ceramic honeycomb filter was set in a measurement cell of Autopore III available from Micromeritics, evacuated, and then pressurized by introducing mercury.
- the relation between a pore size and a cumulative pore volume was determined from pressure when pressurized and the volume of mercury entering pores in the test piece.
- the pore size was calculated from pressure with a contact angle of 130° and a surface tension of 484 dyne/cm.
- the porosity was calculated from the measured total pore volume, with a true specific gravity of cordierite of 2.52 g/cm 3 .
- test piece having a cross section of 4.5 mm x 4.5 mm and a length of 50 mm was cut out of each ceramic honeycomb structure such that it extended substantially along the flow path direction, and heated from room temperature to 800°C at a temperature elevation speed of 10°C/minute under a constant load of 20 g.
- the increase of the longitudinal length of the test piece was measured by a compression load/differential expansion-type thermomechanical analyzer (TMA, ThermoPlus available from Rigaku), to determine its average thermal expansion coefficient (CTE) between 20°C and 800°C.
- TMA compression load/differential expansion-type thermomechanical analyzer
- the isostatic strength test was conducted according to M505-87 of the Japanese Automotive Standards Organization (JASO) issued by the Society of Automotive Engineers of Japan. Each ceramic honeycomb structure was sealed by 20-mm-thick aluminum plates attached to both axial end surfaces, and placed in a pressure vessel with its peripheral surface in contact with a 2-mm-thick rubber. Water was poured into the pressure vessel to exert hydrostatic pressure to the peripheral surface, and the pressure at which the ceramic honeycomb structure was broken was regarded as isostatic strength. The isostatic strength was evaluated by the following standard: Good Not broken even at a pressure of 2 MPa. Fair Broken at a pressure of 1.0 MPa or more and less than 2.0 MPa Poor Broken at a pressure of less than 1.0 MPa.
- JASO Japanese Automotive Standards Organization
- a 0 represents the total area of pores [for example, dark portions in Figs. 7(a) and 7(b) ], and A 0 represents the total area of circles each having a circumference equal to the peripheral length of each pore.
- the ceramic honeycomb structure of the present invention keeps enough strength during use, with smaller pressure loss, it is suitable for large ceramic honeycomb filters of more than 200 mm in outer diameter.
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Claims (8)
- Structure céramique en nid d'abeilles ayant un grand nombre de chemins d'écoulement définis par des parois de cellules poreuses ayant une porosité de plus de 58% et 68% ou moins, et une taille moyenne de pores de 15-32 µm, ladite structure céramique en nid d'abeilles ayant des pores satisfaisant aux conditions suivantes :le volume de pores ayant des diamètres de plus de 50 µm étant supérieur à 10% et 25% ou moins du volume total de pores ;le volume de pores ayant des diamètres de 100 µm ou plus étant 1-8% du volume total de pores ;le volume de pores ayant des diamètres de moins de 10 µm étant 3-10% du volume total de pores ;lesdits pores ayant un écart de distribution de tailles de pores σ [=log(D20)-log(D80)] de 0,45 ou moins, dans laquelle D20 représente une taille de pores (µm) à un volume de pores correspondant à 20% du volume total de pores, et D80 représente une taille de pores (µm) à un volume de pores correspondant à 80% du volume total de pores, dans une courbe montrant la relation entre une taille de pores et un volume cumulé de pores obtenu en accumulant un volume de pores de la taille maximum de pores à une taille particulière de pores, et D80<D20 ; etladite structure céramique en nid d'abeilles comprenant de la cordiérite comme une phase cristalline principale.
- Structure céramique en nid d'abeilles selon la revendication 1, dans laquelle lesdites parois de cellules poreuses ont une perméabilité à l'air de 4x10-12 m2 à 9x10-12 m2.
- Structure céramique en nid d'abeilles selon la revendication 1 ou 2, ayant une résistance isostatique de 1 MPa ou plus.
- Structure céramique en nid d'abeilles selon l'une quelconque des revendications 1-3, dans laquelle lesdites parois de cellules poreuses ont une épaisseur de 0,2-0,3 mm et une densité de cellules de 23-39 cellules/cm2.
- Structure céramique en nid d'abeilles selon l'une quelconque des revendications 1-4, dans laquelle ses phases cristallines contiennent 3-6% de spinelle et 1-8% de cristobalite.
- Structure céramique en nid d'abeilles selon l'une quelconque des revendications 1-5, dans laquelle ladite porosité est supérieure à 59% et 66% ou moins.
- Structure céramique en nid d'abeilles selon l'une quelconque des revendications 1-6, dans laquelle ladite taille moyenne de pores est 20-32 µm.
- Structure céramique en nid d'abeilles selon l'une quelconque des revendications 1-7, qui a un coefficient de dilatation thermique de 3x10-7/°C à 13x10-7/°C entre 20°C et 800°C.
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US20110135873A1 (en) | 2011-06-09 |
CN102089058A (zh) | 2011-06-08 |
KR101648483B1 (ko) | 2016-08-16 |
KR20110048506A (ko) | 2011-05-11 |
EP2335797A1 (fr) | 2011-06-22 |
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